Metal-containing polyazo dyestuffs



r i a 2 Formula II stands for methyl or acyl, the diazotized dyestuffs exhibit greater coupling energy than those amino- METALCQNTAmmG PGLYAZO DYESLTFs trisazo dyestuffs in which x represents hydrogen. The g? g h ef g g gg g f g t? former are obtained by etherizing the hydroxy group of wmer an asslgners e an M W17 5 the acetylaminohydroxybenzene radical with methylzerland yielding agents prior to splitting oil? of the acetyl group,

No Drawing. Filed Dec. 2 1957 Ser. No. 699 949 Claims priority, application Switzerland Dec. 5, 1956 alternatlvely by acylatlng 1t Wlih alkylsulfonyl Claims. (ill. 260-145) arylsulfonyl halides.

The operating procedure of the process is as follows.

The present invention relates to metal-containing poly- 10 The aminotrisazo dyestuffs of Formula H are either azo dyestuffs of the general formula suspended in a dilute mineral acid and directly diazotized,

or in the form of their neutral ammonium, sodium or OMe0 potassium salts they are dissolved in water and indirectly diazotized. The diazo compounds thus obtained are R1'-N=NRlN NR3 N=N az0-R4 preferably filtered and employed in coupling as concen- (D trated aqueous pastes. The diazo compound enters the whereim hydroxynaphthalene 1n the ortho-position to the hydroxy group. Coupling is conducted preferably in alkaline solu- R R and R stand for radicals of the benzene or naphtion and if desired in the presence of organic bases, e.g.

thalene series which together contain at least two pyridine. The metal-free polyazo dyestuff so formed is sulfonic acid groups, isolated by neutralizing the coupling solution and/or salt- R for a naphthalene radical which may be further subing out and filtering. If desired it can be purified by stituted, which contains at least one Water-solubilizing redissolving and reprecipitation.

group and which links the two groups -azoand Metallization is carried out with copperor nickel- OMerin ortho-position to each other, yielding agents, preferably in the presence of ammonia Me for one copper or nickel atom, and organic bases, for example monoor diethanolamine,

, moipholine or pyrid ne. When x stands for a methyl or and where n the nucleus A may be further substituted by acyl group preferab,ly for tha radical of an aliphatic or alkyl or aikOXy' aromatic sulfonic acid group in this case-metallization The dyesmfis must eentam 3 or 4 weter'selublhzmg must be effected under conditions which permit removal groups to render them water'seluble' of these groups. The acyl group can be readily split ofi Especially valuable dyestuffs e e metaleontaining before metallizing by heating the polyazo dyestuif for a pelyaze dyestufis of Formula I m Winch R1 stands for a short time in an alkaline, e.g. soda-alkaline, solution.

naphthalene radical f two Sulfeme aeld greeps In most cases the preferred procedure will be to split off and R2 and R3 Stand for radicals of the benzene Senes' the acyl group in the coupling solution after completion The Process, for the predueuen of h Polyaze e of the coupling reaction giving the polyazo dyestuff.

stuffs and their metalcor nplex compounds cons sts in The new metaLCOntaim-ng polyazo dyestuffs Produced coupling 1 mol of the diazo compound of an anim by the present process possess good solubility in water;

tnsaze dyestufi of the formula 7 their solutions are stable to additions of alkali-metal salts 6 O 40 and to calcium salts. The dyestufis dye animal fibers 5 T1 sgcg as wolol, silk, and alsbc; lilatllller, bin brown to dgray 2 s a es. T. ey possess nota y 'g su stantivity an arc RN=NRFN=N RN=N%/-NH2 (I1) suitable for dyeing and printing fibers of natural or regenerated cellulose such as cotton, hemp, flax, spun viscose Wherem R3 A have the aforeelted meamngs and filament viscose rayon. On these materials they yield and x Stands for hydregenamethyl or acyl, with 1 9 of level shades of brown to gray which are fast to light, hydroxynaphtha'lene wrmeh eouPles erthopesltlen washing and perspiration, and stable to crease-resistant to the hydroxy group which contains at least one w finishing processes. They can be discharged to white selubllizlng group and Whleh be further e with a neutral or alkaline discharge paste. The dyeings and treatmg the resultant tetraklsazofiysswfia Whleh must are only very slightly sensitive to metals; they possess-good eontam the faTouPs e fastness to water, sulfite, formaldehyde, rubbing, Wet sary for water'solublhty Wlth a copper or nfekel'yleldmg pressing, and boiling in neutral and alkaline baths. Their When x Stands f0r methyl e thls group must light and wet fastness can be improved by aftertreatment be split off before or during metallization. with a polyalkylene-p-olyamine in presence of a copper The ammemsazo dyestuffs of general Formula II which salt; this treatment also renders the dyeings fast to scroopare used as reactants can be produced, for example, by ing and Stable to heat couphng the dlazo compounds of ammodlsaze dyestufis of In the following examples the parts and percentages are the general formula by weight and the temperatures in degrees centigrade.

R1-N=NR2-N=NR3NH2 r i E pl 1 7 wherein R R and R have the aiorenamed meanings, -3 Q.S parts ofthe aminotrisazo dyestufi of the formula V SIOaH 00m with N-acetylated o-aminophe-nols in alkaline solution, in the -form of the sodium salt are dissolved in 750 parts upon which the diazo group enters into para-position to of hot water. The solution is cooled to 15 and mixed the hydroxy group of the aminophenol. The acetyl with a concentrated aqueous solution of 3.5 parts of sogroup in the resultant trisazo dyestuif is then split oif. dium nitrite. Then 15 parts of hydrochloric acid 30% When the x in the aminotrisazo dyestufls of general are added to it with constant stirring. The diazo com- Patented Get. 24., 1961.

pound thus formed is obtained as a brown precipitate. After /2 to 1 hour diazotiation is completed. The diazo suspension at 5-10 is then run into a solution of 16 parts of 2-phcnylamino-8-hydroxynaphthalene-6-sulfonic a in the form of the sodium salt are dissolved in 600 parts of hot water. On cooling to 20 the dyestufli is diazotized indirectly according to the particulars of Example 1.

The precipitated diazo compound is then filtered oil. A

acid and 20 Parts Q Sodium caflmnatfi in 200 Parts of 5 solution of 11.2 parts of 2-hydroxynaphthalene-4-sulfonic Y Completion of P P P J dyesmfi acid, parts of sodium carbonate and 50 parts of a is salted out from the react on solution, filtered Off and mixture of pyridine bases in 200 parts of water is cooled Washad with a m 301M101} of Common Saltto 0-5 with ice, and the moist filter cake is added to it I'he filter cake is dissolved in 1600 parts of Water at with thorough stirring completion of coupling the 90 9 co1nvrslon Into the Copper coinplex compound' 10 solution is weakly acidified with hydrochloric acid and To i 50mm) added 50 Parts OI a 25% aquefms the precipitated polyazo dyestufi is filtered off. 501mm of ammOma 25 Parts i g The metal-free polyazo dyestufi is dissolved in 750 Subsequently Concentrated q so upon of 1 parts of Water at 70. The solution is given 10 parts parts of crystallinecopper sulfate is poured into the soluof Sodium acetate and a Solution of 12 5 parts of y tion, and the reaction mixture is stirred at 90 until the 15 tamne CG er 8111f? R and the Whole is stirred for 30 milk methoxy group is Completely Split Off and the copper utes In zl iis Way a copper complex compound is formed P i colilPound of the polyaizo dygstuf-f 1s i i which on drying is obtained as a brown-black powder This is precipitated by the addition of sodium chioride It disrqolv S at I dbr n a d and is then filtered ofi, Washed and dried. t 2 d e i z g b n 1 The copper-containing polyazo dyestutf is a dark brown g e g 2: a i d fi l coforatlon' powder which gives a violettish brown solution in water t as Very a m y or co on an ers o and a blue-violet solution in concentrated sulfuric acid. armed cellulose- It dyes these fibers f f brown It has good amnity for cotton and fibers of regenerated Shades which P Very good 8m f f fastcellulose, and gives fast-to-light dark brown shades which 1168s and good Stablllty t0 cfease-reslstant fimshmg P have good stability to crease-resistant finishing processes. 65 68- Emm [e 2 Further examples are set out in the table below. The p aminotrisazo dyestuffs used as diazo compounds corre- 33 parts of the aminotrisazo dyestutf of the formula Spond to Formula The meanings of R1, R2, R3 and x are given in the appropriate columns; under R R 803E OH and R the basic compounds corresponding to the radicals are named. The next columns contain details of 11 O N N O h N N a the nature and the position of the substituents in the E (3H3 nucleus A, the azo component (a hydroxynaphthalene, which may be substituted), the metal-yielding agent, and 303g 35 the shade of the metal-containing dyestufl on cotton.

Substituent in A Shade of the Ex. R! R2 R; 1 A20 component Metal metal-containing No. (I) (II) (III) (IV) Nattgre lgosi- (VI) (VIIa) di%eStlz%fi%) EL 1011 C0 OD 3 l-aminobenzenc-- l-aniinobenzene-z l-amino-S-methyl- H 2-hydroxynaphtha- Cu Red-brown.

sulfonic acid. sulfonic acid. benzene. lene-fi-earboxylic 8.0 4 rin do -do H CH3 6 2-hydroxynaphtha- Cu Violettishbrown.

lens t-sulfonic 3C1 5 da do fl CH3 Z-hydroxynaphtha- Cu Do.

lene-G-sulfonic acid.

6 do ..do .d0 S|O do Cu Do.

7 n do H Z-benzoylamino-fi- Ou Grayishbrown.

hydroxynaphtha- 1en3-8-sulf0nic 3.01 s rin dn dn H l-hydroxynaphtha- Ni Violettishbrown.

leng-3-sulfonic 2.01 0 do do H OG H 5 l-hydroxynaphtha- Cu Dark reddish leng-ei-sulfonio brown. 3.01 1n fln do do H l-hydroxynaphtha- Ou Dark brown.

- leng-fi-sulfonic 9.01 11 do do S0 -CH 2-llileirdzfylaminloa3l- Cu Violet brown.

0 ap alegs-6301110 2.01 19 rln fin dn H O H 5 l-afietylamililnfigihy- Ou Darkbrown.

o 46132 15 1 2: acid. 1a dn do do 011 5-hydroxy-1.2:1'.2- Ou Gray.

phenonaphthazine-7-su1fonio acid.

Substituent in A Shade of the Ex. R1 R R3 2: Azo com onent Metal metal-containing No. (I) (II) (III) (IV) Nature Posi- (VI (VIIa) dyestufi on (Va) tion cotton (VIIb) 14 1-amin0benzene-4- 1-amin0benzene-2- 1-amin0-3-methyi- CH -hydroxy-1.2:1.2- Cu D0.

sulfonic acid. suiionic acid. benzene phenonaphthazine-4 .7-disulfonic acid. 15.-- 1-amin0benzcne-3- dc do CH3 dc 011 Do.

sulfonic acid. 16"--- 2-amin0naphtha- 1-amino-3-methy1- d0 CH3 2-hydroxynaphtha- Cu Red brown.

1ene-4.8-disu1- benzene. I 1enc-3-carboxy1ic ionic acid. acid. 17 2-amin0naphthado do CH3 Z-hydroxynaphtha- 011 Do.

1ene-6.8-disu1- lene-fi-sulfonic ionic acid. acid. 18 2aminonaphthado do H do Cu Do.

1ene-4.8-disulionic acid. 19 n n H l-hydroxynaphtha- Cu Violettishbrown,

lene-4-sulfonic acid. 20 do d0 .-do H l-hydroxy'naphtha- Ni Do.

lene-5-sulfonic r acid. 21 2-amin0naphthado do H 2-hydroxynaphtha- 011 Do.

1ene-6.8-disu1- 1enc-3.6-disulfonic ionic acid. acid. 22"--. 2-amincnaphthado do H 2-(3-nitro)-benzoy1- Cu Dark brown.

1cne-4.8-disulamino-fS-hydroxyionic acid. naphthalene-8- sulfonic acid. 23 o I n do CH Z-phenylamino-S- Cu D0.

. hydroxynaphthaiene-3,6-disu1- v ionic acid. .do .do H 1-propiony1aminc-8- Cu Violettishbrown,

' hydroxynaphtha- 1ene-4-su1fcnic V acid. 25 dn CH 2-(3-ch10r0)-pheny1- 011 Dark brown.

' amino-S-hydroxynaphthalene-6- sulfonic acid. 26 l-aminonaphthal-aminonaphthal-aminonaphtha H 2-hydr0xynaphtha- Cu Gray-vio1et.

lene-fi-sulfonic lene-fi-sulfonic 1ene-4-sulfonic acid. acid. acid. 27 aminobenzene -.do Cu Brownish violet. 28 1-amino-4-methy1- d0 Cu Do.

benzene. 29 1-aminc-3-ch1oro- 2-(4-methyi)- Cu Gray-violet.

benzene. phenylamino-B- hydroxynaphthaleng-7-sulfonic aci 30.--" l-amino-2.4-dil-aminonaphtha 1-amincnaphtha- CH 2-hydroxynaphtha- ,Cu Brownish violet.

methylbcnzenelenc-7-sulionic lene. lene-G-sulionic fi-sulfonic acid. acid. acid.

31. 1-amino-2- l-aminonaphl-aminonaph- H do Cu Dc methoxy-4- thalene. tha1ene-7- nitrobenzene- Sulicnic acid. s-sulicnic acid. I 32"--. l-aminonaphl-aminonaph- 1-amin0-2- H Z-hydrcxynaphtha- Cu Gray-violet,

thaleneithaiene-G- methoxyben- 1cne-4-Su1ianic sulionic acid. sulfonic acid. Zane. acid 33 l-aminoben- 1-amino-3- 1-amin0-2- CH3 do Cu Dark brown,

zene-2. -dimethyibenmethylbensulionic acid. zene. W zene. 34 do l-aminobenzene.-. 1-amin0-2- H l-hydroxynaphtha- Cu Do.

methoxy-5- lenei-sulionic I methylbenzene. acid. 35 -do l-amino-a-chloro- 1-amin0benzene CH: do Cu Do,

benzene. 36... l-aminobenzenel-aminonaph- 1-am1n0-3- CH: 2bui;yryianiino-5- Cu Gray-violet.

S-Sulionic acid. iha1ene-7- methoxybenhydroxynaphthsulfonic acid. zene. alegeJ-sulfonic aci 37.--" l-aminonaph- 1-amino-2.5- 1-arnino-2.5- CH: 2 benzoylamino-5- Cu Dark brown.

tha1ene-3.6.8- dimethylbendimethylbenhydroxynaphthtrisulionic acid. zene. zene. aleieq-sulionic aci 38.-- l-aminoben- 1-amin0-2.5 l-amino Z- CH 2-(2-ch1or0)-ben- Cu D0.

zene-2A-disuldimethoxyethylbenzene. zoylamino-5-hyionic acid. benzene. droxy-naphth aiene-7'su1fonic acid. 39. l-aminonaphl-amino-B- 1-amino-3- 'CH: Z-hydroxynaphth- Cu Red-brown.

tha1ene-3.6- methox'ybenmethylbenr alene-ficulfonic disulicnic acid. zene. zcne. acid. 40..- l-aminonaph- 1-amino-3- -do CH; Cu D0.

tha1cne3.8- methyibendisuifonic acid. zene. 41 l-aminonaphdo -.d0 CH; -d0 Cu Do.

thaiene-4.8-disulionic acid. V I 42 2-aminonaph- 1-aminc-3- 1-amino-3- CH3 l-hydroxynaphth- Cu Dark brown.

thalene'ljethylbenzene. chlorobenzene. a1ene-5-su1ionic disulionicacid. acid. 43 2-aminonaphtha- 1-amino-3- 1-aminobenzene CH do Cu Do.

lane-3.6-disulmethy1beuzene.- ionicacid. 44 2-aminonaphthado -d0 CH3 2-hydroxynaphtha- Cu Red-brown 1ene-5.7-disullene-G-carboxylic ionic acid.

acid.

Substituent in A Shade of the Ex. R R R 2 Azo component Metal metal-containing N o. (I) (II) (III) (IV) Nature Posi- (VI) (VIIa) dyestufi 011 (Va) tion cotton (VIIb) 45 2-aminonaphthal-aminonaphl-aminonaph- OH; 2-phenylamino-5- Cu Gray.

lene-3.6.8-trithalene. thalene. hydroxynaphthasulfonic acid. leng-7-sulfonic E01 46-.. 2-aminonaphthado do CH; l-benzoylamino-8- Cu D0.

1ene-6.8-disulhydroxynaphthaionic acid. lens-3.6-disu1fonic aci 47".-. l-aminonaphthal-aminonephdo OH; -d 011 D0.

lenefi-snlionic tha1ene-6- acid. sulionic acid. 48 do do l-aminonaph- OH; 01130 l-acetylamlno-S- Cu D0.

thalene-7- hydroxynaphthasulfonic acid. lene--sulfonic acid.

Example 49 brown shade which is fast to light, washing and perspira- 100 parts of cotton fabric are wetted out and entered into a dyebath at 30 composed of 3000 parts of soft water, 2 parts of anhydrous sodium carbonate and 0.6 part of the metal-containing polyazo dyestufi obtainable according to Example 2. An addition of 10 parts of sodium sulfate is made, then the dyebath is heated to 100 in the course of 30 minutes, two additions of 10 parts of sodium sulfate being made at 50 and 70. After reaching 100 the bath is maintained at the same temperature for minutes. At this point another 10 parts of sodium sulfate are added and the bath then allowed to cool. At 50 the dyed cotton is removed, rinsed well in cold water and dried at 60. It is dyed in a dark tion.

A yet higher standard fastness to' light, washing and perspiration is achieved when the dyeing is treated with a polyalkylenepolyamine in presence of a copper salt. After rinsing, the dyed material is entered into an aftertreating bath containing 3000 parts of water and 2 parts of a cupriferous polyalkyleneployamine and treated therein for 30 minutes at 70. The cotton is then removed, rinsed in cold water and dried at The dyeing has very good fastness to light, Washing and perspiration.

Formulae of representative dyestuffs of the foregoing examples are as follows:

Example 1 Hogs- Example 2 IHa CH3 Example 16 S0311 0 CnO COOH CH: O H:

SOQH

SOaH

Example 17 8 05]; Example 18 loin Example 19 SOaH O- Cu-O =N-ON=NON=N N; =N-

(His 0113' S0311 SOaH Example 23 SIOQH 07Ou(|) SO3H CH5 CH3 I Ho8s SOaH I Having thus disclosed the invention what is claimed is:

1. A metal-containing polyazo dyestuff of the formula R represents a naphthalene radical linking both the groups -azoand OMe in ortho-position to each other and which is selected from the group consisting of naphthalene, lower alkanoylaminonaphthalene, benzoylaminonaphthalene, chlorobenzoylaminonaphtha- IRA-Ya lene, nitrobenzoylaminonaphthalene, mononuclear arylaminonaphthalene, and phenonaphthazine.

whereln: 3 represents a water-solubilizing group,

R t d for a member l d fro h group 2 represents a member selected from the group consistsisting of phenyl, mono-, diand tri'substituted phenyl, mg of hydrogen, lower alkyl and lower y,

and a sulfonaphthyl with from one to three sulfonic Me IPTe56Ht$ a member Selected #0111 the group 6011- acid groups, the substituted phenyl being-substituted slstlng of a pp atPIn and a nlckel atom, and with at least one member selected from the group conn Stands for n fi e ntege s 1 and 2. sisting of methyl, methoxy, nitro, sulfonic acid groups 2. A copper-containing polyazo dyestufi which correand chlorine; sponds to the formula V OCu0 I N=N N: N=N 1 1=N-Ri-vm OH: E:

R stands for a member selected from the group conwherein:

sisting of phenyl, monoand (ii-substituted phenyl, R4

. represents a naphthalene radical linking both the naphthyl, and monosulfonaphthyl, the substituted phen groups and in ortho posifion to each yl being substituted with at least one member selected from the group consisting of methyl, ethyl, methoxy, sulfonic acid groups and chlorine;

R stands for a member selected from the group con- 0 sisting of phenyl, monoand di-substituted phenyl, naphthyl and monosulfonaphthyl, the substituted phenother and which is selected from the group consisting of naphthalene, lower :alkanoylaminonaphthalene, benzoylaminonaphthalene, chloro'benzoyl-aminonaphthalene, nitrobenzoylaminonaphtl'ralcne, mononuclear arylaminonaphthalene and phenonaphthazine,

yl being substituted with at least one member selected V tfl11d$ a 9 Selefied from 'f EP P Consistfrom the group consisting of methyl, ethyl, methoxy mg of a sulfonrc -ac1d and a carboxylrc acid group, and and chlorine; m stands for one of the mtegers l and 2. the total number of sulfonic acid groups contained in 3. The copper-containing polyazo dyestuif which cor- R R and R being from two to three; responds to the formula SiOaH O CuO I =NGN=NQN=N N =N CH3 H:

4. The copper-containing polyazo dyestufl which corresponds to the formula 3,005,814 11 12 5. The copper-containing polyazo dyestufl which corresponds to the formula 0 H3 C H3 S|O3H 6. The copper-containing polyazo dyestufi which corresponds to the formula SOsH 0- Cu-(|) OOOH CH3 (7H3 $03K 7. The copper-containing polyazo dyestuff which corresponds to the formula SIO3H O;Cu-O $0311 CH3 Ha HOsS- References Cited in the file of this patent UNITED STATES PATENTS 2,242,456 Dellfs et a1 May 20, 1941 FOREIGN PATENTS 466,545 Canada July 11, 1950 

1. A METAL-CONTAINING POLYAZO DYESTUFF OF THE FORMULA 